Ring opening polymerization with a metathesis catalyst system of cycloolefins is well known. The cycloolefins for purposes herein are selected from monocycloolefins which contain 3 to 9 carbon atoms and which contain 1 to 4 double bonds, and polycycloolefins which contain a norbornene group. The metathesis catalyst system includes a catalyst and a cocatalyst. The catalyst is generally selected from molybdenum and tungsten compounds whereas the cocatalyst is selected from organometallics such as alkylaluminums, alkyltins, alkylaluminum halides, aryloxyalkylaluminum halides, and alkoxyalkylaluminum halides.
U.S. Pat. No. 4,400,340 to Klosiewicz describes a tungsten-containing catalyst such as tungsten halide or tungsten oxyhalide. The catalyst is suspended in a solvent to prevent it from prepolymerizing a monomer to which is added an alcoholic or a phenolic compound to facilitate solubilization of the tungsten catalyst in the monomer and a Lewis base or a chelant to prevent premature polymerization of the solution of the tungsten compound and the monomer. Treatment of the tungsten compound should be carried out in the absence of moisture and air to prevent deactivation of the tungsten compound catalyst. The catalyst must be treated in the manner outlined above in order to render it soluble in the cycloolefin monomer. The cocatalyst in this patent is disclosed as being selected from tetrabutyltin and alkylaluminum compounds such as alkylaluminum dihalide or dialkylaluminum halide where the alkyl group contains 1 to 10 carbon atoms. The preferred alkyl group is ethyl with diethylaluminum chloride being the most preferred cocatalyst. These cocatalysts are sensitive to air and moisture but are readily soluble in the cycloolefin monomers.
U.S. Pat. No. 4,380,617 to Minchak et al discloses metathesis catalyst systems for polymerizing cycloolefins. The catalysts are defined as organoammonium isopolymolybdates and organoammonium isopolytungstates and these catalysts are soluble in cycloolefins and are insensitive to air and moisture. The cocatalysts in this patent are similar to the cocatalysts disclosed in U.S. Pat. No. 4,400,340 and are generally selected from organometallics, particularly alkylaluminum halides although in a less preferred embodiment, other metals can be used in place of aluminum such as lithium, magnesium, boron, lead, zinc, tin, silicon, and germanium. Also, metallic hydrides can be used in whole or in part for the organometallic cocatalysts. Alkylaluminum and the corresponding organometallic compounds can also be used as cocatalysts herein.
U.S. Pat. No. 4,426,502 discloses the use of alkoxyalkylaluminum halides or aryloxyalkylaluminum halides as cocatalysts in metathesis catalyst systems to polymerize cycloolefin monomers. These cocatalysts are disclosed as especially useful in conjunction with organoammonium isopolytungstate and isopolymolybdate catalysts in polymerization of cycloolefins or norbornene-type monomers. By modifying the alkylaluminum halide cocatalysts to alkoxy or aryloxy alkylaluminum halides, the reducing power of the cocatalysts is thus lowered to provide adequate pot life for mixing various ingredients at room temperature, and for work interruptions, before initiation of polymerization and subsequent rapid polymerization.
Organoammonium isopolymolybdate and isopolytungstate catalysts contain molybdenum oxide or tungsten oxide anions, respectively, whereas organoammonium heteropolymolybdates or heteropolytungstate catalysts contain at least one other hetero atom in addition to molybdenum or tungsten.